JPH0741521A - Method for polymerizing cycloolefin - Google Patents

Abstract

PURPOSE:To obtain polynorbornene in a high yield by polymerizing a cycloolefin in the presence of a specific metallocene compound and a promoter. CONSTITUTION:A ligand obtained by bonding (substituted) cyclopentadienyl groups or substituted derivatives thereof through C, Si, Ge, etc., is coordinated to a halide of Ti, Zr, Hf, etc. The coordination compound is hydrogenated at the indenyl or hafnium groups to obtain a metallocene compound comprising the hydrogenated groups bonded to each other. A 5C or higher cycloolefin is polymerized at ordinary pressure to 50kg/cm<2> and 0 to 200 deg.C in the presence of a catalyst comprising the above compound and a promoter.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for polymerizing cyclic olefins. Specifically, it relates to a method for polymerizing a cyclic olefin using a specific metallocene catalyst.

[0002]

2. Description of the Related Art Regarding the polymerization of a polymer having excellent heat resistance by addition-polymerizing a cyclic olefin, W. Kamins
The first method using a catalyst composed of a metallocene compound and aluminoxane by ky et al. (Catalytic Olefin Po
lymerization edited T. Keiiand K. Soga Kodansha 199
0). Further, some of the present inventors have already reported that a cyclic olefin can be polymerized with relatively high activity by using a catalyst containing a metallocene compound having an asymmetric ligand as one component (Japanese Patent Laid-Open No. 3-139506). ).

[0003]

The metallocene catalyst having an asymmetric ligand has a relatively high activity with respect to cyclopentene, but has a problem that the activity is poor when it is applied to the polymerization of norbornene, and further the activity is further deteriorated. Development of improved catalysts is desired.

[0004]

[Means for Solving the Problems] The present inventors have conducted extensive studies on a method for polymerizing a cyclic olefin with high activity per catalyst, which has solved the above problems, and completed the present invention. That is, the present invention is characterized in that a catalyst comprising a hydrogenated metallocene compound having asymmetrical ligands bonded to each other and a cocatalyst is used as a catalyst in a method for polymerizing a cyclic olefin having 5 or more carbon atoms. It is a manufacturing method of polyolefin.

Examples of the monomer to be polymerized in the present invention include cyclic olefins having 5 or more carbon atoms, and norbornenes are particularly preferable. Norbornenes include, in addition to norbornene, those in which a part of hydrogen of norbornene is replaced with other substituents. In the polymerization method of the present invention, particularly, hydrogen at the 5-position is replaced with an alkyl group having 1 to 10 carbon atoms. It can be preferably applied to the above. In the present invention, the metallocene compound having hydrogenated asymmetric ligands bonded to each other is a cyclopentadienyl group or a substituted cyclopentadienyl group and an indenyl group or a fluorenyl group or a substituted derivative thereof is carbon, silicon, or germanium. It can be produced by coordinating a ligand bound with, for example, a halide such as titanium, zirconium, or hafnium, and then hydrogenating the indenyl group or hafnium group by hydrogenating. Here, the group connecting the cyclopentadienyl group or the substituted cyclopentadienyl group and the indenyl group or the fluorenyl group is specifically a methylene group, an ethylidene group, a propylidene group or the like having 1 to 2 carbon atoms.
Preferable examples thereof include an alkylidene group of 0, an aromatic-substituted methylene group having 13 to 30 carbon atoms such as diphenylmethane, dibiphenylmethane, and dinaphthylmethane, and a silylene group such as dimethylsilylene, diethylsilylene, and diphenylsilylene. As the group used by substituting with hydrogen such as cyclopentadienyl group, indenyl group and fluorenyl group, an alkyl group having 1 to 20 carbon atoms and a halogen element such as chlorine, bromine, fluorine and iodine are generally used. The cocatalyst used in combination with these metallocene compounds is preferably aluminoxane, which is a polymer of organoaluminum and water, and a compound that can be a stable anion with alkylaluminum, for example, Lewis acid, stable cation and stable Anion ion pairs and the like are shown as examples, but it is also possible to combine these.

As the alkylaluminum, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum and tributylaluminum, dialkylaluminum halide such as diethylaluminum chloride dipropylaluminum chloride and the like can be preferably used. Examples of the ion pair of Lewis acid or stable cation and stable anion include magnesium chloride, calcium chloride, barium chloride, magnesium fluoride, tetrakisperfluorophenylboron triphenylmethane salt or amine salt, and tetraphenylborane triphenylmethane salt or amine salt. Examples thereof include salts. (For example, EP277003, EP27004, JP-A 1-501950, JP-A 1-502036, etc.) As the polymerization conditions, all the polymerization methods used for the polymerization of ordinary olefins or polymerization of cyclic olefins can be used. The polymerization temperature is 0 to 200 ° C., usually room temperature to 100 ° C., and the polymerization pressure is atmospheric pressure to 50 kg / cm ² . In the present invention, not only cyclic olefin but also copolymerization with ethylene can be used.

[0007]

EXAMPLES The present invention will be further described with reference to the following examples. Example 1 Isopropylidenecyclopentadienylfluorenyl zirconium chloride, synthesized according to J. Am. Chem. Soc., 110, 6255 (1988), was used with PtO ₂ in dichloromethane at room temperature at a hydrogen partial pressure of 100 kg /. 20w of isolopyridene cyclopentadienyl octahydrofluorenyl zirconium chloride obtained by hydrogenation at cm ² and methylaluminoxane (manufactured by Tosoh Corporation, methylaluminoxane polymerization degree 15)
1 ml of a t% solution was dissolved in 5 ml of toluene, 2 ml of norbornene was added, and the mixture was polymerized at 50 ° C. for 1 hour. The reaction solution was then washed twice with 10 ml of 5% sulfuric acid water,
It was discharged into 1 liter of methanol, filtered and dried to obtain 0.4 g of a polymer. The intrinsic viscosity of the polymer was 1.58 and the glass transition temperature measured by DSC was 238 ° C. The measurement results of infrared absorption spectrum are shown in FIG.

Example 2 In place of isopropylidenecyclopentadienyloctahydrofluorenylzirconium chloride, 1 mg of diphenylmethanecyclopentadienyloctahydrofluorenylzirconium dichloride synthesized in the same manner was replaced with isopropylidenecyclopentadienylfluoride. A polymer (0.6 g) was obtained in the same manner as in Example 1 except that nyl zirconium chloride was used instead. The intrinsic viscosity of this polymer was 1.85.

Comparative Example 1 The procedure of Example 1 was repeated except that 1 mg of isopropylidenecyclopentadienylfluorenylzirconium chloride was replaced with isopropylidenecyclopentadienyloctahydrofluorenylzirconium chloride.
Only 03 g of polymer was obtained. The intrinsic viscosity of this polymer was 0.35.

[0010]

EFFECT OF THE INVENTION By carrying out the method of the present invention, polynorbornene can be produced in good yield and is industrially very valuable.

[Brief description of drawings]

1 is an infrared absorption spectrum of polynorbornene obtained in Example 1. FIG.

Claims (1)

[Claims] 1. A method for polymerizing a cyclic olefin having 5 or more carbon atoms, characterized in that a catalyst comprising a hydrogenated metallocene compound having asymmetric ligands bonded to each other and a cocatalyst is used. Method for producing polyolefin.